Role of bond orientational order in the crystallization of hard spheres

Abstract: With computer simulations of the hard sphere model, we examine in detail the microscopic pathway connecting the metastable melt to the emergence of crystalline clusters. In particular we will show that the nucleation of the solid phase does not follow a two-step mechanism, where crystals form inside dense precursor regions. On the contrary, we will show that nucleation is driven by fluctuations of orientational order, and not by the density fluctuations. By considering the development of the pair-excess entropy inside crystalline nuclei, we confirm that orientational order precedes positional order. These results are at odd with the idea of a two-step nucleation mechanism for fluids without a metastable liquid-liquid phase separation. Our study suggests the pivotal role of bond orientational ordering in triggering crystal nucleation.